Triazine derivatives possessing aphicidal properties



United States Patent f 3,169,964 TRIAZINE DERIVATIVES POSSESSINGAPHICIDAL PROPERTIES Alan Calder-bank, Eric Callander Edgar, and JohnArthur Silk, Bracknell, England, assignors to Imperial ChemicalIndustries Limited, Millbank, London, England, a corporation of GreatBritain N0 Drawing. Filed June 24, 1963, Ser. No. 290,196

Claims priority, application Great Britain, Oct. 25, 1957,

33,358/57; Apr. 23, 1959, 13,939/59 11 Claims. (Cl. 260-2493) Thisapplication is a continuation-in-part of Serial No. 764,498 and SerialNo. 21,134, both now abandoned. The entire subject matter of each ofthese prior applications is incorporated herein by reference.

The invention relates to new organic compounds and more particularly itrelates to triazine derivatives which possess valuable aphicidalproperties.

According to the invention therefore we provide s-triazine derivativesof the formula:

R10 NRaRl wherein R and R standfor methyl or ethyl radicals, wherein R RR and R which may be the same or diiferent, stand for hydrogen or forlower alkyl radicals or, R and R or, R and R may be joined, togetherwith the adjacent nitrogen atom, to form a piperidino ring, and whereinX stands for an oxygen or a sulphur .atom, and the salts thereof.

As suitable salts of the said s-triazine derivatives there may bementioned salts derived from inorganic acids for example hydrochloridesand salts derived from organic acids for example oxalates, p-toluenesulphonates, methane sulphonates and isethionates.

As suitable examples of lower alkyl radicals (R R R and R there may bementioned methyl, ethyl, propyl and butyl radicals.

Preferred compounds of the present invention areZ-diethoxy-phosphinothioylthiomethyl-4 S-diarnino-striazine,

Z-diethoxyphosphinylthiomethyl-4 6-diamino-s-triazine,

Z-dimethoxyphosphinothioylthiomethyl-4 6-diamino-striaiiine,

2-dimethoxyphosphinylthiomethyl-4: 6-diamino-s-triazine,

Z-dimethoxy-phosphinothioyllhiomethyl-4-amino-6- methylamino-s-triazineand Z-di-methoxyphosphinothioylthiomethyl-4-amino-6-dimethylamino-s-triazine.

' According to a further feature of the invention we provide a processfor the manufacture of the s-triazine derivatives which comprisesinteraction of a compound of the formula:

wherein R R and X have the meaning stated above and wherein M stands foran alkali metal, for example 3,169,964 Patented Feb. 16, 1965 2 sodium,or an ammonium radical, and a compound of the formula:

NR3R4' %N O Y.OHz-C N RsRa wherein R R R and R have the meanings statedabove and wherein Y stands for a halogen atom.

As a suitable halogen atom there may be mentioned for example chlorine,bromine or iodine. The reaction may be carried out within thetemperature range of 20-150 C. and preferably by heating the reactantstogether in an inert solvent or diluent for example a lower alcohol forexample methanol or ethanol.

The halomethyl-s-triazines used as starting materials may be obtainedeither by interaction of a compound of the formula:

wherein Y has the meaning stated above and R stands for a lower alkylradical, and a corresponding biguanide of the formula:

NRaR4 NRiR a wherein R R R and R have the meaning stated above, providedthat R R R and R do not all stand for alkyl radicals, or by reaction ofthe corresponding diazomethyl-s-triazine derivative with gaseoushydrogen halide for example gaseous hydrogen chloride.

According to a further feature of the invention we provide a process forthe manufacture of some of the s-triazine derivatives which comprisesinteraction of a compound of the formula:

Rgo SCHQOOOR? 3 wherein R R X and M have the meaning stated above, and acompound of the formula:

wherein R and Y have the meaning stated above.

The s-triazine derivatives with which this invention is concernedpossess outstanding selective aphicidal activity. They display very highcontact, residual and systemic properties against aphid species and theyare also of value as aphicidal seed dressings. They are also highlytoxic to certain other injurious insects and mites. They possess lowphytotoxic properties.

Thus according to yet a further feature of the invention we provideinsecticidal compositions containing at least one of the s-triazinederivatives described above, in admixture with suitable diluents orcarriers.

As suitable compositions there may be mentioned for example aqueousformulations wherein the active ingredient, in the form of the base or asalt thereof, is dissolved or dispersed in aqueous media for examplewater which may contain organic solvents for example methanol,tetrahydrofurturyl alcohol or ,B-ethoxyethanol and also suitable wettingor dispersing agents or other suitable auxiliary agents known to the artto be used in the preparation of such aqueous formulations. A suitablewetting or dispersing agent is the condensation product of ethyleneoxide with an alltyl phenol for example the product obtained from thecondensation product of octylcresol with about 78 molecular proportionsof ethylene oxide. Preferred compositions are those containing between0.0001% and 0.1% by weight of active ingredient.

The insecticidal compositions may also be in the form of seed dressingswherein the active ingredient is admixed with an inert pulverulent solidfor example fullers earth, talc, kaolin or bentonite. The said dressingsmay be applied to seeds for example delinted cotton seed at a rate ofbetween 1% and 8% by weight of the seed and the young plants eventuallyobtained from the dressed seed are protected against aphid infestationsfor example against Aphis gossypii.

As stataed above, the s-triazine derivatives possess selective aphicidalproperties and the insecticidal compositions described above showactivity against aphid infestations such as Macrosiphum pz'si and Aphisfabae,

The invention is illustrated but not limited by the following examplesin which the parts are by weight:

Example 1 A mixture of 42 parts of 2-chloromethyl-4:6-diaminos-triazine,57 parts of sodium O:O-diethyl-phosphorothioate and 320 parts of ethanolis stirred and heated under reflux for six hours. It is then allowed tocool and stand for 20 hours and is then filtered. The solid residue thusobtained is boiled with ethanol and the mixture is filtered. Thefiltrate is cooled and there is obtained2-diethoxyphosphinylthiomethyl-l:6-diamino-s-triazine as a crystallineproduct, M.P. 169 C.

The hydrochloride is prepared by dissolving the above compound inalcoholic hydrochloric acid and allowing the solution to stand for a fewminutes. It has M.P. 144146 C. with decomposition and it is readilysoluble in water.

Example 2 8 parts of 2-chloromethyl-4:6-diamino-s-triazine are added toa solution of 10.45 parts of sodium O:O'-diethylphosphorodithioate in 80parts of ethanol and the mixture is stirred and heated under reflux forseven hours. The mixture is cooled and filtered and the solid residue iswashed with water. It is crystallised from ethanol and there is thusobtained 2-diethoxyphosphinothioylthiomethyl-4:6-diamino-s-triazine,M.P. 168169 C.

The hydrochloride may be prepared by passing hydrogen chloride into asolution of the base in ethyl acetate. It has M.P. 174-175 C.

solution of the base in hot ethanol with an equivalent quantity ofoxalic acid dihydrate in acetone and removing the solvents byevaporation. It has M.P. -123 C.

When the 2-chloromethyl4:6-diamino-s-triazine used as starting materialis replaced by an equivalent proportion of 2 chloromethyl426-bis-)dimethylamino)-s-triazine, there is likewise obtained2-diethoxyphosphinothioylthiomethyl 4:6 bis(dimethyl-arnino)-s-triazine,M.P. 60- 62 C.

Example 3 A solution of 14 parts of O:O'-diethyl S-ethoxycarbonylmethylphosphorothiolothionate in 120 parts of methanol is stirred, and a warmsolution of 5 parts of biguanide in 300 parts of methanol is addedgradually during a period of two hours. Stirring is continued for afurther three hours and the mixture is then allowed to stand for afurther sixteen hours. The mixture is filtered and the solid residue soobtained is 2-diethoxyphosphinothioylthiomethyl-4:6-diamino-s-triazine,M.P. 169 0., identical with the product of Example 2.

The O:O'-diethyl S-ethoxycarbonylmethyl phosphorothiolothionate used asstarting material may be obtained as follows:

93 parts of O:O'-diethyl phosphorodithioic acid are added with coolingto a solution of sodium ethoxide (prepared from 11.5 parts of sodium) in240 parts of ethanol. 0.25 part of sodium iodide is added and 61.3 partsof ethyl chloracetate are then run in with stirring during 40 minutes.The mixture is heated under reflux for two hours and is then treatedwith 5 parts of water. The mixture is filtered and the filtrate isevaporated under reduced pressure to remove most of the ethanol. Theresidue is treated with water and ether and the ether extract isseparated, washed twice with water and dried over sodium sulphate. Theether is removed and distillation yields O:O-diethylS-ethoxycarbonylmethylphosphorothiolothionate, B.P. 105107 C./0.005 mm.11 1.4960.

Example 4 A mixture of 8 parts of 2-chloromethyl-4z6-bis(methylamino)-s-triazine, 7.5 parts of sodium O:O'-diethylphosphorothiolate, 160 parts of ethanol and 40 parts of henzene isstirred and heated under reflux for 6 hours. The reaction mixture isallowed to cool and is then filtered The filtrate is evaporated todryness under reduced pressure and the residue is taken up in 67 partsof chloroform. The mixture is filtered and the filtrate is evaporated.The residual solid is crystallised from ethyl acetate and there is thusobtained 2-diethoxyphosphinylthiomethy1-4:6-bis(methy1amino)-s-triazine, M.P. 228 C.

The 2 chloromethyl-4:6-bis(methylamino)-s-triazine used as startingmaterial may be prepared as follows:

33.1 parts of 1:5-dimethylbiguanide dihydrochloride are added to asolution of sodium methoxide prepared from 7.6 parts of sodium and 160parts of methanol. The mixture is heated under reflux for four hours andis then filtered. 20 parts of ethyl chloroacetate are then added to thefiltrate at ordinary temperature during thirty minutes and the solutionis allowed to stand for 16 hours. The mixture is filtered and the solidresidue is crystallised from fl-ethoxyethanol to give2-chloromethyl-4z6- bis(methylamino)-s-triazine, M.P. 228 C.

Example 5 A solution of 15.8 parts of O:O-dimethyl phosphorodithioicacid in parts of methanol is treated with 5.3 parts of anyhdrous sodiumcarbonate. 15.9 parts of 2- chloromethyl-4:6-diamino-s-triazine are thenadded and the mixture is heated under reflux for 7 hours. The reactionmixture is then cooled and filtered and the solid residue is washed withwater and dried. It is crystallised from aqueous methanol or aqueousB-ethoxyethanol and there is thus obtainedZ-dimethoxyphosphinothioylthio- 75 methyl-4:S-diamino-s-triazine, M.P.164-166 C. The hydrogen oxalate may be prepared by mixing a 2.8 parts ofthe above base are dissolved in a solution of 1 partof methanesulphonicacid in parts of water by stirring at 50-60 C. The solution is cooledand filtered and the solid residue soobtained isZ-dimethoxyphosphinothioylthiomethyl-4z6-diamino-s-triazinemethanesulphonate, M.P. 160162 C.

Example 6 A- mixture of-9L2 parts of sodium Ozo -dimethylphosphorothiolate, 8.0 parts of 2-chlor0methyl-4:6-diaminos-triazine,and 65 parts of 'methanol is heated under reflux for 18-hours andthereaction mixture'is then cooled and filtered; The solid;residue is freedfrom sodium chloride by washing with water. It is then crystallised fromwater and there is thus obtainedZ-dimethoxyphosphinylthiomethyll:6-diamino-s-triazine, M.P. 198

Example. 7

6.9 parts of sodiumare reacted with 120 parts of methanol and 19 partsof 1-methylbiguanide hydrochloride are thenadded; The mixture is heatedunder reflux for 3 hours and cooled, and then 24.5 parts of ethylchloroacetate are added slowly over 25 minutes. After standing for anhour thev reaction mixture is filtered and Example 8 7.9 parts ofO:O-dimethylphosphorodithioic acid in 64 parts of methanol areneutralised at a temperature of 20 30 C. bypassing in dry ammonia gaswith cooling. 8.7 parts of 2-chloromethyl-4amino-6-methylamino-s-triazine are then added and the mixture is heatedunder reflux for 90 minutes. The reaction mixture isconcentrated'under'reduced pressure and then filtered and the filtrateis diluted with water and cooled. The aqueous mixture is filtered andthe solid residue is crystallised from aqueous methanol and there isthus obtained Z-dimethoxyphosphinothioylthiomethyl 4amino-6-rnethylamino-striazine, M.P. 126l27 C.

Using an equivalent quantity of 2-chloromethyl-4-amino-6-dimethylamino-s-triazine in place of the2-chloromethyl-4-amino-6-methylarnino-s-triazine used as startingmaterial, thereis obtained in a similar manner, an oil which solidifieson-cooling. It is crystallised from aqueous methanol and there is thusobtained Z-dimethoxyphosphinothioylthiomethyl 4amino-6-dimethylamino-s-triazine, M.P. 77'79 C. The2-chloromethyl-4-amino fidimethylamino-s-triazineused as startingmaterial may be obtained by the process as described in Example 9.

Example 9 ethyl phosphorothiolate areheated under reflux in 80 parts of-ethanol for 7 hours. The reaction mixture is cooled and filtered andthe filtrate is evaporated. The residue is treated with diluteaqueouszethanol and the mixture, is filtered. The solid residue iscrystallised from a mixture of benzene and petroleum ether,(B.P. 6080C.) and there is thus obtained-Z-diethoxy-phosphinylthiomethyl-4-amino-6-dimethylamino-s-triazine, M.P. 92-93 C.

6. Example 10 guanide and. 50 parts of dry pyridine is stirred at atem-.

perature of 18-23 C..for 6 hours and is then allowed to stand for about18 hours. The reaction mixture is filtered and the filtrate isevaporatedunder reduced pressure.

The residue is dissolved in ethanol and. again evaporated to completethe removal of pyridine. residue is recrystallised from isobutanol andthere is thus obtained 2-diethoxyphosphinylthiomethyl-4:6-bis(methylamino)-s-triazine, M.P. 134-136 C., identical with the productdescribed in Example 4.

O O-diethyl"S-ethoxycarbonylmethyl phosphorothiolate may be prepared bythe following procedure:

69 parts ofdiethyl phosphite are added to 320*parts' of alcohol in which11.5 parts oflsodium have been dissolved. 16" parts of sulphurare thenadded in-small portions, so that the temperature does not exceed 50 C.61.4 parts of ethyl chloroacetate are next added, and the reactionmixtureis heated under reflux for 2 hours and then cooled. The bulk ofthe-alcohol is removed by evaporation and the residue is treated.withether and water. The ethereal extract is separated, washed withwater, dried over anhydrous sodium sulphate and t en distilled. There isthus obtained O:O' -diethyl S-ethoxycarbonylmethyl phosphorothiolate,B;P. 96C./0.01 rnm.

Example 11 A- mixtureof 9.5 parts of l:5-dimethyl-biguanide,- 20.4 p

parts of O:O'--diethyl S-ethoxycarbonyl-methyl phosphorothiolothionateand parts of ethanol is stirred at a temperature of 18 -23 C. during 24hours. The mixture is then filteredand the solid residue is washed withethanol. There is thus obtained 2-diethoxyphosphinothioylthiomethyl-4:6-bis- (methylamino -s-triazine, M.P. 131-13 3 C The hydrochlorideofthis base is prepared by dissolving 3 parts of the above compound in20 parts of concentrated aqueous hydrochloric acid and then filteringthereaction mixture after one hour. There is thuso'btained 2-diethoxyphosphinothioylthiomethyl-4 6- bis (methylamino s-triazinehydrochloride, M.P. 134l37 C.

Example 12 Amixture of 6.45 parts of 1-ethylbiguanide, 13.6 parts ofO:O'-diethyl S-ethoxycarbonylmethyl phosphorothioll othionate and 65parts of ethanol is stirred at .a temperature of 1823 C. for 6 hours.

Example 13 11.5 parts .of 1:l-pentamethylenebiguanide hydrochlm ride.are added to a solution of 11.5 parts of sodiumin 400 parts of methanoland the mixture is heated under reflux for 3 hours and then cooled. 61parts of'ethyl chloroacetate are added slowly-during .30 minutes andafter one hour, the mixture is filtered and the solid residue is washedwith water. It is then crystallised from aqueous methanol and thusprovides 2-chlorornethyl-4aamino-6-piperidino-striazine, M.P. l58l60 C.

20.6 partsof this triazine are. added to 'a solution of 17.5 parts ofsodium O:O-diethyl phosphorothiolate in parts .of ethanol and themixture isthen heated under refluxfor 7 hours. Thereaction, mixture isfiltered and the filtrate is evaporated under reduced pressure. The

The crystalline The reaction mixture. is concentrated under reducedpressure and then diluted residual oil is dissolved in ether and theethereal solution is washed with water, dried over anhydrous sodiumsulphate and then evaporated. The residual oil is dissolved in ethanoland the solution is treated with alcoholic picric acid. The mixture isfiltered and the solid residue is crystallised from ethanol. There isthus obtained 2-diethoxyphosphinylthiomethyl 4arnino-G-piperidino-s-triazine picrate, M.P. 166-168 C. When thispicrate is stirred in aqueous ethanol with the hydroxide form ofAmberlite resin IRA-400, there is obtainedZ-diethoxyphosphinylthiomethyl 4 amino-6-piperidino-s-triazine, M.P.1l2114 C.

Example 14 A solution of 2.3 parts of l n-butylbiguanide and 4.0 partsof O:O-diethy1 S-ethoxycarbonylmethyl phosphorothiolothionate in 25parts of ethanol is allowed to stand at a temperature of 18-23 C. for 24hours. The solvent is then removed by evaporation under reduced pressureand the residue is dissolved in ether. The ethereal solution is washedwith water, dried over anhydrous sodium sulphate and evaporated. Theresidual oil is treated with alcoholic picric acid and there is thusobtained the picrate of 2-diethoxy-phosphinothioylthiomethyl 4amino-6-I1- butylamino-s-triazine, M.P. 127-130 C.

Example 15 The process described in Example 1 is repeated except thatthe 2-chloromethyl-4:6-diamine-s-triazine used as starting material isreplaced by an equivalent quantity of2-bromomethyl-4:6-diamino-s-triazine. There is thus obtained in asimilar manner Z-diethoxy-phosphinylthiomethyl-4:6-diarnino-s-triazine,M.P. 169 C., identical with the product obtained in Example 1.

The process described above is repeated except that the 2bromomethyl-4:6-diarnino-s-triazine used as starting material isreplaced by an equivalent quantity of2-iodomethyl-4:6-diamino-s-triazine. There is again obtained, in asimilar manner, 2-diethoxyphosphinylthiomethyl-4:6- diamino-s-triazine,M.P. 169 0., identical with the product obtained in Example 1.

The 2-bromomethyl-4:6-diamino-s-t1'iazine used as starting material isprepared by adding ethyl bromoacetate (167 parts) slowly to biguanide(101 parts) in methanol (800 parts) at C. The mixture is filtered andthe solid residue is crystallised from aqueous alcohol to give thedesired product, M.P. 226229 C. In a similar manner, the use of ethyliodoacetate (214 parts) in place of ethyl bromoacetate gives2-iodomethyl-4z6-diamino-s-triazine, M.P. 182-184 C.

Example 16 80 parts of Z-diethoxyphosphinothioylthiomethyl-4:6-diamino-s-triazine are dissolved in 10,000 parts of methanol and thesolution is poured into 1,000,000 parts of water containing 500 parts ofthe condensation product of octylcresol with 7-8 molecular proportionsof ethylene oxide. When this preparation is sprayed on to broad beanplants which are then infested with Macrosiphum pisi, a 100% kill of thelatter is obtained within 24 hours.

Example 17 8 parts of 2-diethoxyphosphinylthiomethyl 4:6diamino-s-triazine hydrochloride are dissolved in 1,000,000 parts ofwater containing 500 parts of the condensation product of octylcresolwith 7-8 molecular proportions of ethylene oxide. When Macrosz'phum pisiare sprayed with this preparation, 97% of the aphids are killed within24 hours.

Example 18 8 parts of 2-diethoxyphosphinylthiomethyl 4:6diamino-s-triazine are dissolved in 1000 parts of methanol and thesolution is diluted with 100,000 parts of water containing 50 parts ofthe condensation product of octylcresol with 7-8 molecular proportionsof ethylene oxide.

8 When broad bean plants are sprayed with this preparation and theninfested three days later with Aphis fabae, a kill of the aphids resultsindicating that the preparation has marked residual aphicidal activity.

Example 19 1 part of 2-diethoxyphosphinylthiomethyl 4:6diamino-s-triazine is dissolved in 20 parts of methanol and the solutionis poured into 2000 parts of water containing 1 part of the condensationproduct of octylcresol with 7-8 molecular proportions of ethylene oxide.When a pair of leaves half-way up the stem of a broad bean plantinfested with A phis fabae is immersed in this preparation a completekill of aphids above the immersed leaves isobtained in less than 24hours, and below the leaves in two days. There are no phytotoxicsymptoms, and the preparation therefore possesses valuable systemicactivity.

Example 20 A seed dressing is repared by ball-milling equal parts ofZ-diethoxyphosphinylthiomethyl-4:6-diamin0-s-triazine and fullers earthfor 8 hours. Delinted cotton seed is dressed at the rate of 8% by weightwith this preparation before planting. The seedlings eventually obtainedare completely protected against continuous infestation by Aphisgossypii for at least three weeks.

Example 21 100 parts of2-diethoxyphosphinylthiomethyl-4:6-diamino-s-triazine hydrochloride aredissolved in 1,000,000 parts of water containing 500 parts of thecondensation product of octylcresol with 7-8 molecular proportions ofethylene oxide. When some beneficial insects including honey bees,Aphidius species of aphis parasite adults and. pupae, ladybird adultsand larvae, Syrphid fly larvae, and predatory capsids Anthacorisnemorum, are sprayed with this preparation, no kills of the insects areobtained.

Ladybird adults and larvae, and Syrphid fly larvae feeding on aphids areunaffected, while the aphids themselves are killed by the sameconcentration of toxicant.

Example 22 1 part of 2-dimethoxyphosphinothioylthiomethyl-4:6-diamino-s-triazine is dissolved in 5 parts of tetrahydrofurfuryl alcoholat 50 C. and the solution is added to 100,000 parts of water containing50 parts of the condensation product of octylcresol with 7-8 molecularproportion of ethylene oxide. This preparation gives a 100% kill ofMacrosiphum pisi on plants which are sprayed with it.

Example 23 1 part of 2-dimethoxyphosphinothioylthiomethyl-4:6-diamino-s-triazine is added to 5 parts of water containing 0.56 part ofisethionic acid (2-hydroxyethanesulphonic acid) with stirring. Theresulting solution is mixed with 10,000 parts of water containing 5parts of the condensation product of octylcresol with 7-8 molecularproportions of ethylene oxide. Plants sprayed with this solution areprotected against infestation by aphid species.

According to the present invention we also provide new s-triazinederivatives of the formula:

in which R and R are methyl or ethyl radicals; R is a hydrogen atom; R Rand R which can be the same or diiferent, are such a hydrogen atom or amethyl, ethyl, propyl or butyl radical, or R and R together with theiradjacent nitrogen atom constitute a piperidino ring; R is a methyl,ethyl, propyl or butyl radical; and X is an oxygen or a sulphur atom;and acid addition salts thereof.

Compounds which in particular have been found to possess usefulaphicidal activity are those in which the groups R R and R together havea total number of carbon atoms not exceeding six, and especially where Ris a hydrogen atom.

In general, the aphicidal activity of the compounds of the inventiondecreases with increase in the number of carbon atoms in group R; whichis preferably a methyl radical.

The acid addition salts of the present invention can be salts derivedfrom an inorganic acid, for example hydrochlorides, or from an organicacid, for example oxalates, p-toluene sulphonates, methane sulphonatesor isethionates.

The invention also includes a process for the preparation of s-triazinederivatives, in which a compound of the formula:

is reacted with a haloalkyl-s-triazine of the formula:

where R R R R R R R and X have any of the meanings given to them above;M is an atom of an alkali metal, for example sodium, or an ammoniumradical; and Y is a halogen atom, for example bromine. The process ispreferably performed within the temperature range 20-150" C. though thetemperature chosen naturally depends to a large extent upon thereactivity of the reactants. Preferably the reactants are in solution ordispersion in a suitable solvent or filuent, for example water or alower alcohol such as methanol or ethanol.

The haloalkyl s-triazine used as starting material in the processdescribed above can be obtained'by a process in which a compound of theformula:

Y-C H40 0 Rs 1'1.

is reacted with a biguanide of the formula:

N RaR4 HN=G NRBRB where R R R R R and Y have any of the meanings givento them above, and R is a lower alkyl radical, for example methyl orethyl.

The invention also includes pesticidal compositions containing, asactive ingredient, a compound of the invention or an acid addition saltthereof, in admixture with a suitable diluent or carrier. The pesticidalcompositions can, for example, be a liquid composition in which theactive ingredient is dissolved or dispersed in a suitable liquid medium,or it can be a powder composition.

The compounds of the invention have only low solubility in water, butare in general sufficiently soluble to enable aqueous solutions of lowpesticidal concentration to be prepared. However, in order to facilitatethe preparation of aqueous solutions, especially where higher pesticidalconcentrations are required, it has beenfound advantageous to dissolvethe compound initially in a small quantity of methanol,tetrahydrofurfuryl alcohol, diacetone alcohol or fi-ethoxyethanol, andto dilute the resulting organic solution with sufiicient water to obtainthe desired aqueous solution.

Where the pesticidal compositions of the invention is a powdercomposition, the active ingredient can be in admixture with an inertpower diluent, for example fullers 7 l0 earth, talc, kaolin, kieselguhror bentonite. If desired, the pesticidal compositions, whether liquid orsolid, can contain a suitable wetting or dispersing agent or othersuitable auxiliary agent known in the art as being useful in pesticidalcompositions. The powder pesticidal compositions referred to above canbe used as seed dressings- Example 24 This example describes thepreparation of Z-a-(diethoxyphosphinylthio ethyl-4:6-diamino-s-triazine.

Sodium (916 parts) was dissolved inmethanol (200 parts), biguanidesulphate (30 parts) was added, and the mixture heated under reflux withstirring for 3 hours, and then cooled. Ethyl-wbromopropionate (38.1parts) was added as drops to the reaction mixture which was stirred fora further two hours. The solid material obtained was collected byfiltration and thoroughly washed with water, the washed material being2-a-bromo-ethyl- 4:6-diamino-s-triazine, M.P. 223-225 .C. The lattercompound (l9.8 parts) and sodium OO-diethyl phosphorothiolate (19.2parts) were dissolved in absolute ethanol (110 parts) and the solutionheated under reflux for 7 hours after which the mixture was cooled andfiltered, the filtrate concentrated, and then diluted with severalvolumes of water. On standing, 2-a-(diethoxyphosphinylthio)ethyl-4:6-diamino-s-triazine, M.P. 167-9 C. wasobtained as a crystalline product.

This product has been tested and found to be active against the aphidspecies Macrosiphum pisi. The compound was tested in the form of anumber of aqueous solutions covering a range of concentrations, and eachcontaining 0.5% by weight of a wetting agent. Similar aqueous solutionsof various concentrations of the commercial pesticide parathion wereused as a standard for comparison.

The method of testing against M. pisi was as follows:

Adult, apterous, viviparous females were sprayed under a Potter Towerapparatus with '2 cc. of each of the aqueous solutions of the testchemical and of parathion, three replicates of 3040 aphids being usedwith each solution. After being sprayed, the aphids were transferred to2-.oz. jars containing clean broad bean leaves, which were then storedunder conditions of constant temperature and humidity for '24 hours, atthe end of which time the number of dead aphids was counted :and the LD50 value calculated.

Using the LD 50 values obtained for the test chemical and parathion, theparathion equivalent obtained was 2.5, thus illustrating theeifectiveness of the test compound against M. pisi.

Example 25 This example illustrates the activity of the product ofExample 24 against a second aphid species, A phis fabae.

2 a-(diethoxyphosphinylthio) ethyl-4:6-diamino-s-triazine (16 parts) wasdissolved in methanol (1000 parts) and the solution diluted with water(100,000 parts) containing 50 parts of the condensation product ofoctylcresol with 7- 8 molecular proportions of ethylene oxide. Whenbroad bean plants were sprayed with this pesticidal composition and theninfested three days later with A phis fabae, a kill of the aphids wasobtained indicating that the preparation has marked residual aphicidalactivity.

Example 26 The hydrochloride of Z-a-(diethoxyphosphinylthio) 1 lethyl-4:6-diamino-s-triazine was prepared by dissolving the lattercompound in ethyl acetate and passing hydrogen chloride into thesolution. The hydrochloride was obtained as a solid having a meltingpoint of 155-l56 C. with decomposition.

Example 27 This example describes the preparation ofZ-a-(diethoxyphosphinothioylthio) propyl 4.amino--methylamino-s-triazine.

Sodium (2.3 parts) was dissolved in methanol (80 parts), methylbiguanide dihydrochloride (11 parts) was added, and the mixture agitatedat room temperature for thirty minutes. '1 he sodium chloride which hadseparated out was removed by filtration and ethyl a-brornobutyrateparts) added to the filtrate. After standing at room temperature for 24hours the solution was evaporated to dryness leaving a gum, which onrecrystallisation from a mixture of benzene and petroleum ether afforded2-0:- bromopropyl-4-amino-6-methylamino-s-triazine, MP. 66- 70 C. Thelatter compound (2.8 parts) and ammonium OO-dimethyl phosphorodithioate(2.0 parts) were dissolved in methanol (8 parts) and the solution heatedunder reflux for 6 hours and then evaporated to dryness. The residueobtained was dissolved in chloroform and the chloroform solution washedwith water, dried with sodium sulphate and the chloroform removed byevaporation leaving 2 a-(dimethoxyphosphinothioylthio-)propyl-4-amino-6- methylamino-s-triazine as a non-crystallisable gum.

This product was tested against the aphid species 9 Macrosiphum pisi bythe method described in Example 24, and the parathion equivalent wasfound to be 0.8 thus indicating a good degree of protection against theaphids.

Example 28 This examples describes the preparation ofZ-a-(diethoxyphosphinylthio) -n-amyl 4: 6-diamino-s-triazine.

Biguanide (2.9 parts) and ethyl a-bromohexoate (6.4 parts) weredissolved in methanol parts) and the solution allowed to stand at roomtemperature for 2 weeks.

This example illustrates the efiectiveness of the hydrochloride ofExample 26 against the aphid species M. pisi.

2 a-(diethoxyphosphinylthio) ethyl-4:6-diamino-s-triazine hydrochloride(16 parts) was dissolved in water (1 million pants) containing 500 partsof the condensation product of octylctresol with 7-8 molecularproportions of ethylene oxide. When broad bean plants infected withMacrosiphum pisi were sprayed with this pesticidal composition, of theaphids were killed within 24 hours.

What we claim is:

-1. A compound selected from the group consisting of a triazine which infree base form has the formula:

wherein R and R are selected from the group consisting of methyl andethyl; R and R are selected from the group consisting of hydrogen, loweralkyl and, taken together, the atoms necessary to form a piperidinoring; R and R are selected from the group consisting of hydrogen, loweralkyl and, taken together, the atoms necessary to form a piperidinoring; R is selected from the group consisting of hydrogen and loweralkyl; and X is an atom selected from the group consisting of oxygen andsulfur atoms, and the acid addition salts thereof.

2. 2 dimethoxy-phosphinothioylthiomethyl 4:6-diamino-s-trlazlne.

3. 2 diethoxy phosphinothioylthiomethyl-4:6-diamino-s-triazine.

4. 2 diethoxyphosphinylthiomethyl 4: 6-diamino-s-triazrne.

5. 2 dimethoxyphosphinylthiomethyl 4:6-diamino-striazine.

6. 2 dimethoxyphosphinothioylthiomethyl-4-amino-6-methylamino-s-triazine.

7. 2 dimethoxyphosphinothioylthiomethyl 4 amino-6-dimethylamino-s-triazine.

8 2 on (diethoxyphosphinylthio)ethyl 4:6-diaminos-triazine.

9. 2 a (diethoxyphosphinylthio)ethyl 4:6-diaminos-triazinehydrochloride.

1O. 2 a (dimethoxyphosphinylthio) n-amyl-4z6-diammo-s-triazine.

11. 2 c: (dimethoxyphosphinothioylthio)propyl 4-amino-G-methylamino-s-triazine.

References Cited in the file of this patent UNITED STATES PATENTS2,822,364 Schuller Feb, 4, 1958 2,848,451 Schuller Aug. 19, 19582,887,432 Baker et al May 19, 1959 2,911,337 Uhlenbroek et a1. Nov. 3,1959

1. A COMPOUND SELECTED FROM THE GROUP CONSISTING OF A TRIAZINE WHICH INFREE BASE FORM HAS THE FORMULA: